CN106831444A - A kind of valeronitrile hydro-reduction synthesizes the method for n-amylamine - Google Patents
A kind of valeronitrile hydro-reduction synthesizes the method for n-amylamine Download PDFInfo
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- CN106831444A CN106831444A CN201611120406.9A CN201611120406A CN106831444A CN 106831444 A CN106831444 A CN 106831444A CN 201611120406 A CN201611120406 A CN 201611120406A CN 106831444 A CN106831444 A CN 106831444A
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- valeronitrile
- catalyst
- amylamine
- reduction
- hydro
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- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 42
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 150000002815 nickel Chemical class 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 16
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 abstract description 16
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 238000006561 solvent free reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000001816 cooling Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000005070 sampling Methods 0.000 description 10
- 238000009413 insulation Methods 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- -1 titanium modified aluminium oxide Chemical class 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 229960001484 edetic acid Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- YWKRGLREGGAHDC-UHFFFAOYSA-N dichloro(pentyl)borane Chemical compound CCCCCB(Cl)Cl YWKRGLREGGAHDC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of method that valeronitrile hydro-reduction synthesizes n-amylamine, comprise the following steps：(1) valeronitrile is added in the reactor；(2) it is passed through N2Enter line replacement, Ni-based supported catalyst or Ni-based composite catalyst are added in above-mentioned reactor；(3) stirring, logical hydrogen, temperature reaction are opened；(4) reaction terminates, and Filtration of catalyst obtains target product.In the presence of the present invention is with valeronitrile as raw material, with Ni-based supported catalyst or Ni-based supported catalyst and a small amount of ammonia, lead to hydrogen reduction in the absence of solvent, beam is connect as raw material solvent-free reaction to hydrogen is inhaled with valeronitrile, conversion ratio 100%, target product selection rate 95% or so, diamylamine and triamylamine 5% or so, the selectivity of significantly larger than existing valeronitrile method and other method.During hydro-reduction synthesis amylamine, the formation of adjusting process condition control accessory substance diamylamine and triamylamine, is the key of solve problem while generation object as much as possible.
Description
Technical field
The present invention relates to a kind of new synthetic method of valeronitrile downstream product n-amylamine, refer in particular to valeronitrile as raw material, with
The method that Ni-based supported catalyst and the logical hydrogen reduction high yield pulp1 of New Nickel based composite catalyst prepare n-amylamine, belongs to fine chemistry industry
Technical field.
Background technology
N-amylamine is a kind of important chemical intermediate, be widely used in synthesis medicine, dyestuff, solvent, anticorrosive,
The many-sides such as emulsifying agent, antioxidant, flotation agent and thiofide.
The synthetic method of n-amylamine has many kinds, typically several to have：Valeral method, amide method, valeronitrile method and n-amyl alcohol
Method.Wherein, valeral method selectivity about 48%, azide method selectivity about 88%, amide method selectivity about 81%, valeronitrile method selection
Rate about 71% and two n-pentyl boron chloride methods selectivity about 93% etc..
Above method is disadvantageous in that：
Every kind of method target product has considerable amount of accessory substance to produce while generation, be required to subsequent purification separation,
Yield is not high and increased cost；Some methods have used explosion risk article (azide method), the raw materials used cost mistake having
(two n-pentyl boron chloride methods) high.
Existing valeronitrile method selectivity about 71%, it produces the two of about 30% or so while hydro-reduction generates n-amylamine
Amylamine and triamylamine, it is necessary to through diamylamine and triamylamine in rectification and purification removal final product, can just obtain pure target and produce
Thing n-amylamine.This will cause that reaction yield is low, production cost is high, and produce the more three wastes simultaneously.
The content of the invention
For the above-mentioned technical problem of prior art, it is an object of the invention to provide a kind of valeronitrile hydro-reduction synthesis positive penta
The method of amine, its technical process simply, without any solvent, and basic three wastes is produced, using commercially available Ni-based supported catalyst
During agent conversion ratio be 100%, selectivity be more than 95%, use the present inventor synthesize Ni-based composite catalyst when conversion ratio for
100%, selectively reach more than 99%.
To reach above-mentioned purpose, the present invention is achieved by the following technical solutions：
A kind of valeronitrile hydro-reduction synthesizes the method for n-amylamine, comprises the following steps：
(1) valeronitrile is added in the reactor；
(2) it is passed through N2Enter line replacement, Ni-based supported catalyst or Ni-based composite catalyst are added in above-mentioned reactor；
(3) stirring, logical hydrogen, temperature reaction are opened；
(4) reaction terminates, and Filtration of catalyst obtains target product；
The Ni-based composite catalyst of the step (2) is obtained by following steps：
Be dissolved in soluble nickel salt in solvent and be configured to solution by (2-1)；
Be put into shaping carrier with pore structure in solution obtained in step (2-1) and impregnate by (2-2), before obtaining catalyst
Body；
(2-3) reduces the catalyst precarsor in step (2-2)；
Catalyst precarsor after (2-4) reduces step (2-3) is dried, and obtains Ni-based composite catalyst.
Described step (2-1) is by auxiliary agent, surfactant and soluble nickel salt is miscible that solution is configured in solvent；
The mass percent that the auxiliary agent accounts for Ni-based composite catalyst is 5~10%, and the surfactant accounts for Ni-based composite catalyst
Mass percent be 1~10%.
Described auxiliary agent is the mixture of ethylenediamine tetra-acetic acid, diethylamine and triethylamine, and described surfactant is poly-
One or several mixing of oxirane triblock copolymer, polyethers F-201, PEG-8 00 or PEG20000
Thing, described soluble nickel salt is nickel nitrate, nickel acetate or nickel sulfate.
In described step (2-2), after catalyst precarsor is taken out from the container for filling solution, remaining nickel in container
Salt accounts for mass fraction≤10% of the soluble nickel salt total amount of addition, and after dipping is complete, the catalyst precursor for obtaining is done
Dry, drying temperature is 50~100 DEG C.
In described step (2-3), catalyst precarsor is reduced in the reductant solution under inert gas shielding, its
In, the pH of reductant solution is 8~14, and concentration is 0.01~0.1g/ml.
Described Ni-based supported catalyst or Ni-based composite catalyst can be applied mechanically more than ten times.
The synthetic reaction equation of the n-amylamine is as follows：
Beneficial effects of the present invention are as follows：
Valeronitrile hydro-reduction of the present invention synthesizes the method for n-amylamine, with valeronitrile as raw material, with Ni-based supported catalyst and less
In the presence of amount ammonia, hydrogen reduction is led in the absence of solvent, hydrogen pressure is 1.0MPa-2.0MPa, and hydrogenation temperature is 90-
Under the conditions of 110 DEG C, beam is connect as raw material solvent-free reaction to hydrogen is inhaled with valeronitrile, conversion ratio 100%, target product selection rate 95% are left
The right side, diamylamine and triamylamine 5% or so, the selectivity of significantly larger than existing valeronitrile method and other method.In hydro-reduction
During synthesis amylamine, adjusting process condition control accessory substance diamylamine and 3 penta while generation object as much as possible
The formation of amine, is the key of solve problem.
The present invention is controlled in 8~14 OK range the pH of reductant solution when Ni-based composite catalyst is prepared,
Ni can either be made2+Reduction is complete, and suitable rate of reduction can be kept again, generates the metal nickel particle of nanoscale, and can prevent
Only metal nickel particle is reunited because growing up, so as to obtain the loading type nickel-based catalyst of high activity.Ni-based being combined of the invention is urged
Agent has significant difference when in use with market purchasing nickel-base catalyst：Suppress diamylamine and three by being not required to addition alkaline assistant
The generation of amylamine, and selectivity is more than 99%.And the nickel-base catalyst of several models of market purchasing when being not added with alkaline assistant just
The selectivity of amylamine only has 75% or so level, and its best level is also less than 95% after adding auxiliary agent.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
Ni-based supported catalyst in the present invention is the model SN- of the triumphant new material Science and Technology Ltd. production of upper Hisoon
The Ni-based supported catalyst of powder of 5000P.
Embodiment 1 and 2：The preparation of Ni-based composite catalyst
Used catalyst carrier is and purchases from the market in example 1 below -6, is only lived so that titanium is modified in embodiment 1-6
As a example by property alumina support, silica supports：
Embodiment 1
(1) preparation of solvable nickel salt solution：In weighing the beaker of nickel nitrate 300g inputs 1L, add 150ML deionized waters,
150ML absolute ethyl alcohols, stir molten clear；Add auxiliary agent ethylenediamine tetra-acetic acid 5g, diethylamine 15g, triethylamine 20g, surfactant
PEG800 5g, PEG100005g stirring are molten clear standby；
(2) preparation of catalyst precarsor：During the titanium modified aluminium oxide supports 600g of outsourcing put into above-mentioned normal temperature solution
Aeration-drying at 80 ± 1 DEG C is taken out in baking oven after 2 days 2 nights of dipping, and to obtain precursor 700g standby.
(3) catalyst precarsor reduction：100g precursors are fitted into the reactor of 2L, the sodium borohydride of 0.05mol/l is put into
Solution buries precursor, adds a small amount of NaOH regulation pH14, opens reaction at 70 ± 1 DEG C of stirring intensification, has been reacted after 2 hours
Entirely.
(4) catalyst precarsor after reduction is filtered in being dried at 80 ± 1 DEG C, obtains the new valeronitrile reduction of support type special
Ni-based composite catalyst about 100g.
Embodiment 2
(1) preparation of solvable nickel salt solution：In weighing the beaker of nickel nitrate 300g inputs 1L, add 150ML deionized waters,
150ML absolute ethyl alcohols, stir molten clear；Add auxiliary agent ethylenediamine tetra-acetic acid 5g, diethylamine 15g, triethylamine 20g, surfactant
PEG800 5g, PEG100005g stirring are molten clear standby；
(2) preparation of catalyst precarsor：Large aperture silica supports (particle diameter 1-3mm) 600g of outsourcing is put into
To state impregnate in normal temperature solution and take out after 2 days 2 nights in baking oven aeration-drying at 80 ± 1 DEG C to obtain precursor 700g standby.
(3) catalyst precarsor reduction：100g precursors are fitted into the reactor of 2L, the sodium borohydride of 0.05mol/l is put into
Solution buries precursor, adds a small amount of NaOH regulation PH14, opens reaction at 70 ± 1 DEG C of stirring intensification, has been reacted after 2 hours
Entirely.
(4) catalyst precarsor after reduction is filtered in being dried at 80 ± 1 DEG C, obtains the new valeronitrile reduction of support type special
Nickel-base catalyst about 100g.
In embodiment 1 and 2, directly shaping carrier is impregnated in the solution containing soluble nickel salt, the work in catalyst
Property component in the pore structure of shaping carrier can high degree of dispersion, thus dipping after without heat treatment, can be effectively prevented from live
Property component sinter at relatively high temperatures, avoid active metal particles from becoming big and influence catalytic performance；Catalyst after dipping
The loading type nickel-based catalyst of shaping is directly prepared after precursor reduction, and without subsequent forming technique of the prior art, is subtracted
Waste of the active component nickel in forming process is lacked, has improved the utilization rate of Raney nickel, without follow-up calcination procedure, had
The agglomeration of active component is avoided to effect, so as to be effectively improved the catalytic performance of loading type nickel-based catalyst.
Embodiment 3-6：N-amylamine is prepared using Ni-based composite catalyst obtained in embodiment 1 and 2
Embodiment 3
Valeronitrile 500ml, Ni-based composite catalyst 25g obtained in input embodiment 1 and 2 are put into the autoclave of 1L, is led to
Nitrogen is replaced three times, and slowly 100 ± 5 DEG C of reactions are warmed up to after opening stirring, logical hydrogen to required pressure.Inhale the unobvious rear insulation reaction of hydrogen
Sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reaction solution 488ml, n-amylamine 99.79%, diamylamine
0.13%th, triamylamine 0.08%.
Embodiment 4
Valeronitrile 500ml, Ni-based composite catalyst 20g obtained in input embodiment 1 and 2 are put into the autoclave of 1L, is led to
Nitrogen is replaced three times, and slowly 100 ± 5 DEG C of reactions are warmed up to after opening stirring, logical hydrogen to required pressure.Inhale the unobvious rear insulation reaction of hydrogen
Sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reaction solution 488ml, n-amylamine 99.82%, diamylamine
0.11%th, triamylamine 0.07%.
Embodiment 5
Valeronitrile 500ml, Ni-based composite catalyst 20g obtained in input embodiment 1 and 2 are put into the autoclave of 1L, is led to
Nitrogen is replaced three times, and slowly 100 ± 5 DEG C of reactions are warmed up to after opening stirring, logical hydrogen to required pressure.Inhale the unobvious rear insulation reaction of hydrogen
Sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reaction solution 481ml, n-amylamine 99.36%, diamylamine
0.43%th, triamylamine 0.21%.
Embodiment 6
Valeronitrile 500ml, Ni-based composite catalyst 20g obtained in input embodiment 1 and 2 are put into the autoclave of 1L, is led to
Nitrogen is replaced three times, and slowly 100 ± 5 DEG C of reactions are warmed up to after opening stirring, logical hydrogen to required pressure.Inhale the unobvious rear insulation reaction of hydrogen
Sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reaction solution 488ml, n-amylamine 99.52%, diamylamine
0.36%th, triamylamine 0.12%.
In embodiment 3-6, Ni-based composite catalyst can be applied mechanically more than ten times.Reaction equation is as follows：
From embodiment 3-6, when the process step of the invention uses Ni-based composite catalyst, conversion ratio is 100%, choosing
Selecting property reaches more than 99%.
Embodiment 7-12：N-amylamine is prepared using commercially available Ni-based supported catalyst
Embodiment 7
Valeronitrile 500ml, market purchasing nickel-base catalyst 25g are put into the autoclave of 1L, is led to nitrogen and is replaced three times, opened and stir
Mix, lead to ammonia to internal pressure 0.5Kg/cm2Slowly 100 ± 5 DEG C of reactions are warmed up to after leading to hydrogen to required pressure again.Inhale the unobvious rear guarantor of hydrogen
Temperature reaction sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reaction solution 478ml, n-amylamine 94.81%,
Diamylamine 3.73%, triamylamine 1.46%.
Embodiment 8 puts into valeronitrile 500ml, market purchasing nickel-base catalyst 25g in the autoclave of 1L, leads to nitrogen displacement three
It is secondary, open stirring, logical ammonia to internal pressure 0.5Kg/cm2Slowly 100 ± 5 DEG C of reactions are warmed up to after leading to hydrogen to required pressure again.Inhale hydrogen not
Insulation reaction sampling in 1 hour can't detect valeronitrile i.e. cooling discharge after substantially, leaches catalyst and obtains reaction solution 488ml, n-amylamine
94.50%th, diamylamine 4.73%, triamylamine 0.77%.
Embodiment 9 puts into valeronitrile 500ml, market purchasing nickel-base catalyst 25g in the autoclave of 1L, leads to nitrogen displacement three
It is secondary, open stirring, logical ammonia to internal pressure 0.5Kg/cm2Slowly 100 ± 5 DEG C of reactions are warmed up to after leading to hydrogen to required pressure again.Inhale hydrogen not
Insulation reaction sampling in 1 hour can't detect valeronitrile i.e. cooling discharge after substantially, leaches catalyst and obtains reaction solution 490ml, n-amylamine
94.12%th, diamylamine 5.43%, triamylamine 0.45%.
Embodiment 10 puts into valeronitrile 500ml, market purchasing nickel-base catalyst 25g in the autoclave of 1L, leads to nitrogen displacement three
It is secondary, open stirring, logical ammonia to internal pressure 0.1Kg/cm2Slowly 110 ± 5 DEG C of reactions are warmed up to after leading to hydrogen to required pressure again.Inhale hydrogen not
Insulation reaction sampling in 1 hour can't detect valeronitrile i.e. cooling discharge after substantially, leaches catalyst and obtains reaction solution 481ml, n-amylamine
95.31%th, diamylamine 3.63%, triamylamine 1.06%.
Embodiment 11 puts into valeronitrile 500ml, market purchasing nickel-base catalyst 25g in the autoclave of 1L, leads to nitrogen displacement three
It is secondary, open stirring, logical ammonia to internal pressure 0.1Kg/cm2Slowly 110 ± 5 DEG C of reactions are warmed up to after leading to hydrogen to required pressure again.Inhale hydrogen not
Insulation reaction sampling in 1 hour can't detect valeronitrile i.e. cooling discharge after substantially, leaches catalyst and obtains reaction solution 468ml, n-amylamine
95.21%th, diamylamine 4.56%, triamylamine 0.23%.
Embodiment 12 puts into valeronitrile 500ml, market purchasing nickel-base catalyst 25g in the autoclave of 1L, leads to nitrogen displacement three
It is secondary, open stirring, logical ammonia to internal pressure 0.1Kg/cm2Slowly 110 ± 5 DEG C of reactions are warmed up to after leading to hydrogen to required pressure again.Inhale hydrogen not
Insulation reaction sampling in 1 hour can't detect valeronitrile i.e. cooling discharge after substantially, leaches catalyst and obtains reaction solution 468ml, n-amylamine
95.51%th, diamylamine 3.46%, triamylamine 1.03%.
In embodiment 7-12, Ni-based supported catalyst can be applied mechanically more than ten times.Reaction equation is as follows：
From embodiment 7-12, when the process step of the invention uses commercially available Ni-based supported catalyst, conversion ratio is
100%, selectivity is more than 95%.
Comparative example 1
N-amylamine is prepared using traditional preparation technology, it is selectively between 70-80%.
Above-described embodiment is only used for illustrating inventive concept of the invention, rather than the restriction to rights protection of the present invention,
All changes for carrying out unsubstantiality to the present invention using this design, all should fall into protection scope of the present invention.
Claims (8)
1. a kind of method that valeronitrile hydro-reduction synthesizes n-amylamine, it is characterised in that comprise the following steps：
(1) valeronitrile is added in the reactor；
(2) it is passed through N2Enter line replacement, Ni-based supported catalyst or Ni-based composite catalyst are added in above-mentioned reactor；
(3) stirring, logical hydrogen, temperature reaction are opened；
(4) reaction terminates, and Filtration of catalyst obtains target product.
2. the method that valeronitrile hydro-reduction as claimed in claim 1 synthesizes n-amylamine, it is characterised in that the step (2) it is Ni-based
Composite catalyst is obtained by following steps：
Be dissolved in soluble nickel salt in solvent and be configured to solution by (2-1)；
Be put into shaping carrier with pore structure in solution obtained in step (2-1) and impregnate by (2-2), obtains catalyst precarsor；
(2-3) reduces the catalyst precarsor in step (2-2)；
Catalyst precarsor after (2-4) reduces step (2-3) is dried, and obtains Ni-based composite catalyst.
3. the method that valeronitrile hydro-reduction as claimed in claim 2 synthesizes n-amylamine, it is characterised in that：Described step (2-1)
It is by auxiliary agent, surfactant and soluble nickel salt is miscible that solution is configured in solvent；The auxiliary agent accounts for Ni-based composite catalyzing
The mass percent of agent is 5~10%, and the mass percent that the surfactant accounts for Ni-based composite catalyst is 1~10%.
4. the method that valeronitrile hydro-reduction as claimed in claim 3 synthesizes n-amylamine, it is characterised in that：Described auxiliary agent is second two
The mixture of amine tetraacethyl, diethylamine and triethylamine, described surfactant is PEO triblock copolymer, polyethers
One or several mixtures of F-201, PEG-8 00 or PEG20000, described soluble nickel salt are nitric acid
Nickel, nickel acetate or nickel sulfate.
5. the method that valeronitrile hydro-reduction as claimed in claim 2 synthesizes n-amylamine, it is characterised in that：Described step (2-2)
In, after catalyst precarsor is taken out from the container for filling solution, in container remaining nickel salt account for addition soluble nickel salt it is total
Mass fraction≤10% of amount, after dipping is complete, the catalyst precursor for obtaining is dried, and drying temperature is 50~100 DEG C.
6. the method that valeronitrile hydro-reduction as claimed in claim 2 synthesizes n-amylamine, it is characterised in that：Described step (2-3)
In, catalyst precarsor is reduced in the reductant solution under inert gas shielding, wherein, the pH of reductant solution is 8~14,
Concentration is 0.01~0.1g/ml.
7. the method that valeronitrile hydro-reduction as claimed in claim 1 synthesizes n-amylamine, it is characterised in that：Described Ni-based load is urged
Agent or Ni-based composite catalyst can be applied mechanically more than ten times.
8. the method that valeronitrile hydro-reduction as claimed in claim 1 synthesizes n-amylamine, it is characterised in that the synthesis of the n-amylamine
Reaction equation is as follows：
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810766A (en) * | 2006-01-04 | 2006-08-02 | 四川大学 | Nitrile reducing process to prepare amine |
| US20130177839A1 (en) * | 2010-10-27 | 2013-07-11 | N.E. Chemcat Corporation | Reduction catalyst comprising palladium-gold alloy |
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2016
- 2016-12-08 CN CN201611120406.9A patent/CN106831444A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810766A (en) * | 2006-01-04 | 2006-08-02 | 四川大学 | Nitrile reducing process to prepare amine |
| US20130177839A1 (en) * | 2010-10-27 | 2013-07-11 | N.E. Chemcat Corporation | Reduction catalyst comprising palladium-gold alloy |
Non-Patent Citations (1)
| Title |
|---|
| EDWARD J.SCHWOEGLER等: "Preparation of certain amines", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
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Application publication date: 20170613 |